JP2007246681A - Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc - Google Patents

Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc Download PDF

Info

Publication number
JP2007246681A
JP2007246681A JP2006071995A JP2006071995A JP2007246681A JP 2007246681 A JP2007246681 A JP 2007246681A JP 2006071995 A JP2006071995 A JP 2006071995A JP 2006071995 A JP2006071995 A JP 2006071995A JP 2007246681 A JP2007246681 A JP 2007246681A
Authority
JP
Japan
Prior art keywords
pvc
gas
fuel gas
cao
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2006071995A
Other languages
Japanese (ja)
Inventor
Fumiyoshi Saito
文良 齋藤
Kibu Cho
其武 張
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tohoku University NUC
Original Assignee
Tohoku University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tohoku University NUC filed Critical Tohoku University NUC
Priority to JP2006071995A priority Critical patent/JP2007246681A/en
Publication of JP2007246681A publication Critical patent/JP2007246681A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fuel gas, by which the fuel gas such as hydrogen or methane can simply be produced from wastes such as PVC wastes with waste heat of about 200°C without producing an injurious gas. <P>SOLUTION: This method for producing the fuel gas such as hydrogen or methane gas without by-producing an injurious gas is characterized by adding an oxide such as CaO to PVC (polyvinyl chloride) wastes, crushing the mixture, immobilizing chlorine in the PVC with CaO, and heating the product at about 200°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ＰＶＣの常温脱塩素処理産物から低温加熱により水素やメタンなどの燃料ガスを発生させることに関するものである。 The present invention relates to generating a fuel gas such as hydrogen or methane from a room temperature dechlorination product of PVC by low temperature heating.

従来、水素などのガス発生法には加熱法、触媒法、電気分解法などがある。いずれも優れた方法であるが、装置と操作に一定の工夫が必要であり、必ずしも容易ではない。原料には種々の材料が用いられるが、本発明に対抗するとすればＰＶＣがあり、これから水素やメタンガスなどを発生させるにはその分解温度以上での加熱が必要になる。しかし、この加熱法では有害な塩化水素ガスが発生し、これを除去する必要があるし、温度は最低でも250℃以上必要である。   Conventionally, gas generation methods such as hydrogen include a heating method, a catalyst method, and an electrolysis method. Although both are excellent methods, a certain device is required for the apparatus and operation, and it is not always easy. Various materials are used as the raw material, but if there is a conflict with the present invention, there is PVC, and in order to generate hydrogen, methane gas, and the like from this, it is necessary to heat above its decomposition temperature. However, this heating method generates harmful hydrogen chloride gas, which must be removed, and the temperature must be at least 250 ° C.

また、ＰＶＣをＣａＯなどと混合し、常温で粉砕（メカノケミカル処理）すると、ＰＶＣは脱塩素されることが知られている（例えば、特許文献１）が、この先行文献はメカノケミカル処理後に水洗濾過し、固体残渣と水溶性塩化物を再利用するものあり、水洗工程や分離工程が煩雑であるという問題点がある。   In addition, it is known that PVC is dechlorinated when PVC is mixed with CaO or the like and pulverized at normal temperature (mechanochemical treatment) (for example, Patent Document 1). There is a problem that the solid residue and the water-soluble chloride are reused by filtration, and there is a problem that the washing step and the separation step are complicated.

特開平１１−１２４４６３号公報Japanese Patent Laid-Open No. 11-124463

本発明の目的は、本発明は、有害ガスの発生が無く、かつ、 200℃程度の廃熱で、簡単にＰＶＣなどの廃棄物から水素やメタンなどの燃料ガスを発生できる手法を提供することにある。   An object of the present invention is to provide a method that can easily generate fuel gas such as hydrogen and methane from waste such as PVC with no waste gas generation and waste heat of about 200 ° C. It is in.

本発明によれば、ＰＶＣ（ポリ塩化ビニール）を酸化物と混合し、常温で粉砕（メカノケミカル処理）しＰＶＣを脱塩素化し、しかる後に、その産物を２５０℃以下の温度に加熱することを特徴とするＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法得られる。   According to the present invention, PVC (polyvinyl chloride) is mixed with an oxide, pulverized at room temperature (mechanochemical treatment) to dechlorinate PVC, and then the product is heated to a temperature of 250 ° C. or lower. A method for generating fuel gas from a room temperature dechlorination product of PVC is obtained.

また、本発明によれば、前記酸化物が、ＣａＯであることを特徴とするＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法が得られる。   Further, according to the present invention, there can be obtained a method for generating fuel gas from a room temperature dechlorination product of PVC, wherein the oxide is CaO.

また、本発明によれば、前記ＰＶＣが、廃棄ポリ塩化ビニール成形品のものであることを特徴とするＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法が得られる。   Moreover, according to this invention, the said PVC is a thing of a waste polyvinyl chloride molded article, The generation | occurrence | production method of the fuel gas from the normal temperature dechlorination treatment product of PVC characterized by the above-mentioned is obtained.

ＰＶＣとＣａＯを混合して室温で粉砕すると、メカノケミカル反応が起こり、炭化水素とＣａＯＨＣｌが生成する。これで、ＰＶＣ中の塩素（Cl）はＣａＯＨＣｌとして固定され安定になる。一方、ＰＶＣからClを取り去った残りの炭化水素は、結合状態が緩くなり、容易に熱分解する。ここで、通常のＰＶＣの熱分解温度は最低でも250℃であるが、上記の脱塩素後の炭化水素では200℃程度でも容易に熱分解し、水素やメタンガスを発生する。従って、本発明により、有害ガスの発生も無く、水素やメタンなどの可燃性ガスが発生が可能である。   When PVC and CaO are mixed and pulverized at room temperature, a mechanochemical reaction occurs and hydrocarbons and CaOHCl are generated. Thus, chlorine (Cl) in PVC is fixed and stabilized as CaOHCl. On the other hand, the remaining hydrocarbon from which Cl has been removed from PVC becomes loosely bonded and easily thermally decomposes. Here, the thermal decomposition temperature of ordinary PVC is at least 250 ° C., but the hydrocarbon after dechlorination is easily pyrolyzed even at about 200 ° C. to generate hydrogen and methane gas. Therefore, according to the present invention, no harmful gas is generated, and a combustible gas such as hydrogen or methane can be generated.

以下、本発明の実施の形態について説明する。本発明者の知見に依れば、ＰＶＣ廃棄物にＣａＯを添加して粉砕処理し、ＰＶＣ中の塩素をＣａＯによって固定化し、その後、その産物を200℃程度で加熱するだけで、有害ガスの発生も無く、簡単に水素やメタンガスを発生できる。これらのガスは発電用エネルギーであり、簡単にコジェネレーションシステムが構築できる。図1には、粉砕と加熱操作のフローを示す。   Embodiments of the present invention will be described below. According to the knowledge of the present inventor, CaO is added to the PVC waste and pulverized, the chlorine in the PVC is fixed with CaO, and then the product is heated at about 200 ° C. There is no generation and hydrogen and methane gas can be generated easily. These gases are energy for power generation, and a cogeneration system can be easily constructed. FIG. 1 shows the flow of grinding and heating operations.

ＣａＯを脱塩素材として使用した場合（加熱過程でのキャリアガス：Heガス）まず、ＰＶＣとＣａＯの混合物を遊星ミルにより粉砕する。このときのＣａＯの添加割合は、少なくてもＰＶＣ中のCl全量を固定するに必要な量とする。勿論、ＣａＯ添加率が多いほど脱塩素率が上がるが、混合物量を一定とする場合はＰＶＣ量は少なくなる。また、粉砕処理時間が長いほど脱塩素率は向上するが、最適値があり、それを考慮し、ここでは1〜4時間処理する実験とした。室温で粉砕操作にもかかわらずＰＶＣ−ＣａＯ間での固相反応が生じ、生成物はＣａＯＨＣｌ（塩化物）と有機物（ＰＶＣから塩素が除去されたもの）となる。この混合物を200℃程度に加熱しても、ＣａＯＨＣｌは分解しないので、塩素ガス発生はない。一方、有機物（ＰＶＣ）から塩素が除去されたもの）は塩素がないし、結合もダメージを受けており、容易にH2ガスなどが生成しやすい状態になっている。   When CaO is used as a desalting material (carrier gas in heating process: He gas) First, a mixture of PVC and CaO is pulverized by a planetary mill. At this time, the addition ratio of CaO is at least the amount necessary to fix the total amount of Cl in the PVC. Of course, the higher the CaO addition rate, the higher the dechlorination rate. However, when the amount of the mixture is constant, the amount of PVC decreases. In addition, the longer the pulverization time, the better the dechlorination rate, but there is an optimum value. In consideration of this, the experiment was conducted for 1 to 4 hours. In spite of the pulverization operation at room temperature, a solid-phase reaction occurs between PVC and CaO, and the product becomes CaOHCl (chloride) and organic matter (those from which chlorine is removed from PVC). Even when this mixture is heated to about 200 ° C., CaOHCl is not decomposed, so that no chlorine gas is generated. On the other hand, the organic substance (PVC) from which chlorine is removed) has no chlorine, the bond is damaged, and H2 gas is easily generated.

加熱操作においては、廃熱を利用することを考えると、温度は２５０℃以下であり、雰囲気の制御は重要である。発生するガスの分析ではキャリアガスとしてHeガスを用い、一定流量で実験した。なお、実用化する場合は、真空または窒素ガス雰囲気が望ましい。   In the heating operation, considering the use of waste heat, the temperature is 250 ° C. or lower, and the control of the atmosphere is important. In the analysis of the generated gas, helium gas was used as a carrier gas and an experiment was performed at a constant flow rate. For practical use, a vacuum or nitrogen gas atmosphere is desirable.

ＣａＯを脱塩素材として用いた場合の粉砕処理の有無によるガス発生状況をHeガスをキャリアガスとしての分析結果を表１にしめした。

Figure 2007246681
Table 1 shows the results of analysis using He gas as a carrier gas in terms of gas generation status with and without pulverization when CaO is used as a desalting material.
Figure 2007246681

実施例１ではＣａＯ（脱塩素材）について説明したが。ＣａＯの代わりにLa2O3などでも同様の効果が得られる。La2O3を脱塩素材として用いた場合の粉砕処理の有無によるガス発生状況を表２に示した。キャリアガスはHeガスである。

Figure 2007246681
Although Example 1 explained CaO (desalted material). Similar effects can be obtained with La 2 O 3 or the like instead of CaO. Table 2 shows the gas generation status with and without pulverization when La 2 O 3 is used as the desalting material. The carrier gas is He gas.
Figure 2007246681

表１および２から明らかに、本発明の方法によれば、燃料として有用なEthyleneガス、Ethaneガス、Propyleneガス、Propaneガスが得られることがわかる。   From Tables 1 and 2, it is apparent that Ethylene gas, Ethane gas, Propylene gas, and Propane gas useful as fuel can be obtained by the method of the present invention.

図１は、本発明の粉砕と加熱操作のフロー図である。FIG. 1 is a flow diagram of the grinding and heating operation of the present invention.

Claims (3)

ＰＶＣ（ポリ塩化ビニール）を酸化物と混合し、常温で粉砕（メカノケミカル処理）しＰＶＣを脱塩素化し、しかる後に、その産物を２５０℃以下の温度に加熱することを特徴とするＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法。   PVC (polyvinyl chloride) is mixed with an oxide, pulverized at room temperature (mechanochemical treatment) to dechlorinate PVC, and then the product is heated to a temperature of 250 ° C. or less. A method for generating fuel gas from dechlorinated products. 前記酸化物が、ＣａＯであることを特徴とする請求項１に記載のＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法。   The said oxide is CaO, The generation method of the fuel gas from the normal temperature dechlorination treatment product of PVC of Claim 1 characterized by the above-mentioned. 前記ＰＶＣが、廃棄ポリ塩化ビニール成形品のものであることを特徴とする請求項１または２に記載のＰＶＣの常温脱塩素処理産物からの燃料ガスの発生方法。   The method for generating fuel gas from the room temperature dechlorination product of PVC according to claim 1, wherein the PVC is a waste PVC molded article.
JP2006071995A 2006-03-16 2006-03-16 Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc Pending JP2007246681A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006071995A JP2007246681A (en) 2006-03-16 2006-03-16 Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2006071995A JP2007246681A (en) 2006-03-16 2006-03-16 Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc

Publications (1)

Publication Number Publication Date
JP2007246681A true JP2007246681A (en) 2007-09-27

Family

ID=38591318

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2006071995A Pending JP2007246681A (en) 2006-03-16 2006-03-16 Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc

Country Status (1)

Country Link
JP (1) JP2007246681A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113754924A (en) * 2021-08-12 2021-12-07 重庆文理学院 Method for treating PVC (polyvinyl chloride) based on cooperation of mechanochemical method and industrial solid waste
WO2022043655A1 (en) * 2020-08-26 2022-03-03 Ucl Business Ltd Production of inorganic salts

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124463A (en) * 1997-10-24 1999-05-11 Fumiyoshi Saito Non-thermal dechlorination of polyvinyl chloride
JPH11222534A (en) * 1998-02-06 1999-08-17 Nippon Zeon Co Ltd Process for treating vinyl chloride resin waste
JP2001049267A (en) * 1999-08-10 2001-02-20 Ishikawajima Harima Heavy Ind Co Ltd Plastic gasification method and apparatus therefor
JP2001172427A (en) * 1999-12-17 2001-06-26 Sumitomo Metal Ind Ltd Method for dehalogenation of organohalogen-containing plastic
JP2001191051A (en) * 2000-01-12 2001-07-17 Akira Yoshikawa Method for manufacturing dechlorinated waste plastic
JP2005330437A (en) * 2004-05-21 2005-12-02 City Net:Kk Method and system for processing waste plastic and gas electric power generation system using waste plastic
JP2006131652A (en) * 2004-11-02 2006-05-25 Shinshu Univ Method for making waste plastic material mixture containing chlorine-containing resin harmless

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11124463A (en) * 1997-10-24 1999-05-11 Fumiyoshi Saito Non-thermal dechlorination of polyvinyl chloride
JPH11222534A (en) * 1998-02-06 1999-08-17 Nippon Zeon Co Ltd Process for treating vinyl chloride resin waste
JP2001049267A (en) * 1999-08-10 2001-02-20 Ishikawajima Harima Heavy Ind Co Ltd Plastic gasification method and apparatus therefor
JP2001172427A (en) * 1999-12-17 2001-06-26 Sumitomo Metal Ind Ltd Method for dehalogenation of organohalogen-containing plastic
JP2001191051A (en) * 2000-01-12 2001-07-17 Akira Yoshikawa Method for manufacturing dechlorinated waste plastic
JP2005330437A (en) * 2004-05-21 2005-12-02 City Net:Kk Method and system for processing waste plastic and gas electric power generation system using waste plastic
JP2006131652A (en) * 2004-11-02 2006-05-25 Shinshu Univ Method for making waste plastic material mixture containing chlorine-containing resin harmless

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022043655A1 (en) * 2020-08-26 2022-03-03 Ucl Business Ltd Production of inorganic salts
CN113754924A (en) * 2021-08-12 2021-12-07 重庆文理学院 Method for treating PVC (polyvinyl chloride) based on cooperation of mechanochemical method and industrial solid waste

Similar Documents

Publication Publication Date Title
Zhuo et al. Upcycling waste plastics into carbon nanomaterials: A review
CA2523318C (en) Method to recapture energy from organic waste
SA518400252B1 (en) Method for Generating or Recovering Materials through Smoldering Combustion
WO2004096456A9 (en) Method to recapture energy from organic waste
KR102158694B1 (en) Dechlorination apparatus and method for converting low grade fuel oil into low chlorine clean light fuel oil
JP2010106133A (en) Process and apparatus for making waste into fuel
WO2010119972A1 (en) Btl fuel production system and method for producing btl fuel
Devasahayam Opportunities for simultaneous energy/materials conversion of carbon dioxide and plastics in metallurgical processes
KR102588840B1 (en) Apparatus and method of hydrogen production from reforming of plastic waste by microwave plasma torch
MX2020013186A (en) Chemical processing utilizing hydrogen containing supplemental fuel for catalyst processing.
JP2007246681A (en) Method for producing fuel gas from ordinary temperature dechlorination treatment product of pvc
JP4304237B2 (en) Gasification method of organic matter
CN109563008A (en) A kind of method and system for capturing and recycling for carbon
JP2003253037A (en) Method for dechlorinating chlorine-containing synthetic resin
KR101383320B1 (en) Method for Energizing Waste by Using the Technology of Hydrothermal and recycling of inner energy and System Thereof
EP3434753B1 (en) Process for the production of methane from refuse-derived fuel
US20080102013A1 (en) Providing h2o2 from sulfuric acid, which arises during the combustion of fossil fuels and from sulfur residues contained therein, and using the h2o2 as an energy carrier
Tongamp et al. Generation of hydrogen from polyvinyl chloride by milling and heating with CaO and Ni (OH) 2
JP2009030071A (en) Method for gasifying organic substance
JP7069892B2 (en) Hydrogen production method
JP2009067649A (en) Method for decomposing ammonia
CN114729277A (en) Method for reducing organic material to produce methane and/or hydrogen
JP2005279361A (en) Method for treating waste
JP2003221203A (en) Method for manufacturing hydrogen using waste as raw material
JPH0559371A (en) Method for pyrolyzing carbonaceous material utilizing radiation

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20081107

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20110909

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110913

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20120124